O(S)(NH) Trifluoromethyl-aryl phosphonates

ABSTRACT

New compounds having the generic formula: ##EQU1## wherein R can be selected from the group consisting of hydrogen, alkyl and aryl; R 1  is alkyl; R 2  can be selected from hydrogen, alkyl, alkylcyano, thioalkyl, alkynyl, benzothiazolo, imidazolo, aryl and substituted aryl with the substituents being selected from nitro, alkyl, halogen, cyano, thioalkyl, haloalkyl and amido; X can be oxygen, sulfur or amino, provided that when X is oxygen or sulfur R 2  is other than hydrogen. Compounds of the present invention are active insecticides and miticides.

This is a division of application Ser. No. 298,979 filed on Oct. 19,1972, now U.S. Pat. No. 3,862,999 issued Jan. 28, 1975, which is adivisional application of Ser. No. 123,467 filed on Mar. 11, 1971, nowabandoned.

DESCRIPTION OF THE INVENTION

This invention is directed to a novel group of compounds which may begenerally described as phosphorous derivatives which are activeinsecticides and miticides. The compounds of the present invention arerepresented by the generic formula: ##EQU2## wherein R can be selectedfrom the group consisting of hydrogen, alkyl and aryl; R₁ is alkyl; R₂can be selected from hydrogen, alkyl, alkylcyano, thioalkyl, alkynyl,benzothiazolo, imidazolo, aryl and substituted aryl with thesubstituents being selected from nitro, alkyl, halogen, cyano,thioalkyl, haloalkyl and amido; X can be oxygen, sulfur or amino,provided that when X is oxygen or sulfur R₂ is other than hydrogen.

In general, the above-noted compounds can be prepared by reacting anappropriate alcohol with ethylthionophosphone sulfide to form a reactivemercaptan. The mercaptan is then treated with a halide compound in thepresence of a base such as triethylamine to form the end product. In thealternative, an appropriate alcohol can be reacted with adihalothiophosphonous derivative to obtain a reactive thiochloridatephosphonous intermediate which is reacted with an appropriate compoundto form the end product.

In order to illustrate the merits of the present invention, thefollowing examples are provided:

EXAMPLE 1 O-crotyl-S-propargyl, ethylphosphonodithioate

12.4 GRAMS (0.05 MOLE) OF ETHYLTHIONOPHOSPHINE SULFIDE IS COMBINED WITH200 ML. OF DIOXANE IN A 600 ML. BEAKER. The mixture is stirred at roomtemperature and 7.2 grams (0.1 mole) of crotyl alcohol is added and theresulting mixture is stirred until a clear solution is obtained. Thesolution is cooled in an ice bath to 10°C. and 11.9 grams (0.1 mole) ofpropargyl bromide is added followed by the addition of 10.1 grams (0.1mole) of triethylamine over a period of 10 minutes. The resultingmixture is stirred at room temperature for 1 hour, then poured into 300mls. of benzene. The benzene mixture is washed with 200 ml. of water,100 ml. of saturated sodium bicabonate solution followed by two 100 ml.portions of water. The benzene phase is dried over anhydrous magnesiumsulfate and evaporated under reduced pressure to yield 17.2 grams ofproduct. n_(D) ³⁰ - 1.5375.

EXAMPLE 2 O-allyl-O-ethylphosphorothiochloridate

54 g. (0.5 mole) of allyl alcohol, 56 g. (0.5 mole) of potassiumt-butoxide and 500 ml. of tetrahydrofuran is combined and heated underreflux for 1 hour. The resulting solution is cooled to room temperatureand is added over a period of one hour to a stirring solution of 89.5 g.(0.5 mole) of ethyldichlorothiophosphonate. The reaction temperatureduring the addition is maintained at -10° to -5°. After the addition iscomplete, the mixture is allowed to warm to room temperature and isstirred for 1 hour. The mixture is then poured into 500 ml. of benzeneand washed with three 300 ml. portions of water. The benzene phase isdried with anhydrous MgSO₄ and evaporated under reduced pressure toyield 101 g. of the desired product. n_(D) ³⁰ - 1.5347.

EXAMPLE 3 O-allyl-O-(3-methyl-4-nitrophenyl)-ethylphosphonothioate

9.2 grams (0.06 mole) of 3-methyl-4-nitrophenol is combined with 2.4grams (0.06 mole) of caustic and 20 ml. of water in a 500 ml.three-necked flask fitted with a stirrer, thermometer, and droppingfunnel. The mixture is stirred and 11.1 grams (0.06 mole) of thecompound of Example 2 in 200 ml. of tetrahydrofuran is added over aperiod of 30 minutes. The resulting mixture is stirred and heated underreflux for 2 hours, cooled and poured into 400 ml. of benzene. Thebenzene mixture is washed with 200 ml. of water, 200 ml. of dilutecaustic solution, followed by two 200 ml. portions of water. The benzenephase is dried with anhydrous MgSO₄ and evaporated under reducedpressure to yield 7.7 grams of product. n_(D) ³⁰ - 1.5380.

Other compounds were prepared in an analogous manner starting with theappropriate materials as outlined above. The following is a table ofcompounds representative of those embodied by the present invention.Compound numbers have been assigned to them and are used foridentification throughout the balance of the specification.

                  TABLE I                                                         ______________________________________                                        ∥                                                                    R--CH=CH--CH.sub.2 --O--P--X--R.sub.2                                         |                                                                    R.sub.1                                                                       Com-                                                                          pound                                                                         No.    X      R          R.sub.1                                                                            R.sub.2                                         ______________________________________                                        1      S      CH.sub.3   C.sub.2 H.sub.5                                                                    CH.sub.2 --C.tbd.CH                             2      S      CH.sub.3   C.sub.2 H.sub.5                                                                    CH.sub.2 --SC.sub.2 H.sub.5                     3      S      CH.sub.3   C.sub.2 H.sub.5                                                                    CH.sub.2 --C.tbd.N                              4      S      H          C.sub.2 H.sub.5                                                                    CH.sub.2 --C.tbd.CH                             5      S      H          C.sub.2 H.sub.5                                                                    CH.sub.2 --C.tbd.N                              6      S      H          C.sub.2 H.sub.5                                                                    CH.sub.2 --SC.sub.2 H.sub.5                     7      S                 C.sub.2 H.sub.5                                                                    CH.sub.2 --C.tbd.N                              8      S                 C.sub.2 H.sub.5                                                                    CH.sub.2 --C.tbd.CH                             9      O      CH.sub.3   C.sub.2 H.sub.5                                      10     O      CH.sub.3   C.sub.2 H.sub.5                                      11     S      CH.sub.3   C.sub.2 H.sub.5                                      12     O      CH.sub.3   C.sub.2 H.sub.5                                      13     O      CH.sub.3   C.sub.2 H.sub.5                                      14     O      CH.sub.3   C.sub.2 H.sub.5                                      15     S      H          C.sub.2 H.sub.5                                      16     O      H          C.sub.2 H.sub.5                                      17     S      H          C.sub.2 H.sub.5                                      18     S      CH.sub.3   C.sub.2 H.sub.5                                      19     S      CH.sub.3   C.sub.2 H.sub.5                                      20     O      CH.sub.3   C.sub.2 H.sub.5                                      21     O      H          C.sub.2 H.sub.5                                      22     O      H          C.sub.2 H.sub.5                                      23     O      H          C.sub.2 H.sub.5                                      24     S      H          C.sub.2 H.sub.5                                      25     O      CH.sub.3   C.sub.2 H.sub.5                                      26     S      H          C.sub.2 H.sub.5                                      27     O      CH.sub.3   C.sub. 2 H.sub.5                                     28     O      H          C.sub.2 H.sub.5                                      29     O      H          C.sub.2 H.sub.5                                      30     O      H          C.sub.2 H.sub.5                                      31     O      H          C.sub.2 H.sub.5                                      32     O      H          CH.sub.3                                             33     O      H          CH.sub.3                                             34     S      H          CH.sub.3                                             35     S      H          CH.sub.3                                             36     O      CH.sub.3   CH.sub.3                                             37     O      CH.sub.3   CH.sub.3                                             38     S      CH.sub.3   CH.sub.3                                             39     S      CH.sub.3   CH.sub.3                                             40     S      CH.sub.3   CH.sub.3                                             41     S      CH.sub.3   CH.sub.3                                             42     S      H          CH.sub.3                                             43     S      H          CH.sub.3                                             44     NH     CH.sub.3   C.sub.2 H.sub.5                                                                    H                                               45     NH     CH.sub.3   C.sub.2 H.sub.5                                                                    CH.sub.3                                        46     O      CH.sub.3   CH.sub.3                                                                           CH.sub.2 C.tbd.CH                               47     S      CH.sub.3   C.sub.2 H.sub.5                                      48     S      H          C.sub.2 H.sub.5                                      49     S      H          C.sub.2 H.sub.5                                                                    O                                                                             ∥                                                                    C--NH.sub.2                                     50     O      H          C.sub.2 H.sub.5                                                                    N                                               51     S      CH.sub.3   CH.sub.3                                                                           --∠                                                                     S                                               52     O      H          CH.sub.3                                             53     O      CH.sub.3   CH.sub.3                                             54     O      H          CH.sub.3                                             55     O      CH.sub.3   CH.sub.3                                             56     O      CH.sub.3   CH.sub.3                                                                           O                                                                             ∥                                                                    CNH.sub.2                                       57     O      CH.sub.3   CH.sub.3                                             58     O      CH.sub.3   CH.sub.3                                             59     O      H          CH.sub.3                                             ______________________________________                                    

Entomological Testing Methods I. House Fly [Musca domestica (L.)]

A stock solution containing 100 μg/ml of the toxicant in an appropriatesolvent is prepared. Aliquots of this solution are combined with one ml.of an acetone-peanut oil solution in a dish, 55 mm in diameter, andallowed to dry. The aliquots are varied to achieve desired toxicantconcentrations ranging from 100 μg per dish to that at which 50%mortality is obtained. The dishes are placed in a circular cardboardcage, closed on the bottom with cellophane and covered on top with clothnetting. Twenty-five female house flies are introduced into the cage andthe percent mortality is recorded after 48 hours. LD-50 values areexpressed in terms of μg per 25 male flies.

II. German Cockroach [Blattella germanica (Linne)]

Ten one-month old nymphs are placed into a circular cardboard cagesealed on one end with cellophane and covered by cloth netting on theother. Aliquots of the toxicant, dissolved in an appropriate solvent,are diluted in water to which has been added 0.0002% of a conventionalwetting agent such as polyoxyethylene sorbitan monolaurate ether ofalkylated phenols blended with organic sulfonates. Test concentrationsrange from 0.1% to that at which 50% mortality is obtained. Each ofthese aqueous suspensions are sprayed onto the insects, through thecloth netting, by means of a hand spray gun. Percent mortality isrecorded after 72 hours and the LD-50 values are expressed as percent oftoxicant in the aqueous spray.

III. Lygus Bug [Lygus hesperus (Knight)]

Same as for the German cockroach (II) except that the testconcentrations range from 0.05% to that at which 50% mortality isobtained.

IV. Salt-marsh Caterpillar [Estigmene acrea (Drury)]

Test solutions are prepared in an identical manner and concentrationsare the same as those for the German cockroach (II). Sections of bitterdock (Rumex obtusifolius) leaves, 1-1.5 inches in length are immersed inthe test solutions for 10-15 seconds and placed on a wire screen to dry.The dried leaf is placed on a moistened piece of filter paper in a petridish and infested with five third-instar larvae. Mortality of the larvaeis recorded after 72 hours and the LD-50 values are expressed as percentactive ingredient in the aqueous suspensions.

V. Beet Armyworm [Spodoptera exigua (Hubner)]

Same as salt-marsh caterpillar (IV) except that leaves of Romainelettuce (Latuca sativa) are used as the host plant.

VI. Tobacco Budworm [Heliothis virescens (F.)]

Same as for Beet armyworm (V).

VII. Black Bean Aphid [Aphis fabae (Scop.)]

Nasturtium (Tropaeolum sp.) plants, approximately 2-3 inches tall, aretransplated into sandy loam soil in 3-inch clay pots and infested with50-75 aphids of mixed ages. Twenty-four hours later they are sprayed, tothe point of runoff, with aqueous suspensions of the toxicant. Thesuspensions are prepared as in previously described tests. Testconcentrations ranged from 0.05% to that at which 50% mortality isobtained. Mortality is recorded after 48 hours and the LD-50 values areexpressed as percent active ingredient in the aqueous suspensions.

VIII. Two-spotted Mite [Tetranychus urticae (Koch)]

Same as for the black bean aphid (VII) except that pinto beans(Phaseolus sp.) are utilized as the host plant rather than nasturtiums.

IX. Systemic Tests

A. Black bean aphid:

Aliquots of the toxicant dissolved in an appropriate solvent areincorporated into 1 pound samples of sandy loam soil and placed into 1pint ice-cream cartons. Test concentrations range from 10 ppm oftoxicant per pound of soil down to that at which 50% mortality isobtained. Nasturtium (Tropaeolum sp.) plants approximately 2-3 inchestall are transplanted into the treated soil and infested with 50-75aphids of various ages. Mortality is recorded 72 hours afterinfestation, and LD-50 values are expressed as ppm of active ingredientper pound of soil.

B. Two-spotted mite:

Preparation of the test solution and concentrations is the same as forthe salt-marsh caterpillar test. Pinto bean (Phaseolus sp.) plants withexpanded primary leaves are placed in the solution so that the roots andmajor portions of the stem are completely immersed. Immediately after,the leaves are infested with 75-100 mites of various ages. Mortality ofadults, nymphs and eggs is recorded after one week, and LD-50 values areexpressed as ppm of toxicant in the aqueous suspensions.

                                      TABLE II                                    __________________________________________________________________________                                                     Two-Spotted Mites            Compound                                                                            HF    GR   LB    BA    BAS  SMC  BAW  TBW  PE   Eggs                                                                              Sys                 No.   μg %    %     %     ppm  %    %    %    %    %   %                   __________________________________________________________________________    1     5     .03  .005  .003  10   .03  .03  .01  .03  >.05                                                                              >10                 2     7     .03  .003  .003  5    .01  .03  .03  .03  >.05                                                                              >10                 3     8     .03  .005  .001  10   .1   .1   .01  .03  >.05                                                                              >10                 4     7     .05  .01   .03   3    .03  .01  .03  .005 >.05                                                                              3                   5     7     .03  .001  .003  .8   .03  .03  .003 .005 .05 .8                  6     10    .03  .008  .003  3    .08  .01  .008 .001 .03 .3                  7     100   >.1  >.05  .05        >.1  >.1       .01  >.05                                                                              >10                 8     30    >.1  >.05  >.05       >.1  >.1       .03  >.05                                                                              >10                 9     5     .003 .003  .0003 8    .01  .008 .03  .01  >.05                                                                              >10                 10    7     .01  .003  .003  >10  .1   .01  .01  .01  >.05                                                                              >10                 11    30    .08  .03   .003  >10  .03  .03  .01  .03  .05 >10                 12    6     .03  .003  .001  >10  .05  >.1  .01  .01  >.05                                                                              >10                 13    30    >.1  .03   .001  >10  .08  >.1  .05  .05  >.05                                                                              >10                 14    30    .1   >.05  .03   >10  >.1  .1   .03  >.05 >.05                    15    20    .01  .005  .005  8    .005 .01  .001 .03  >.05                                                                              >10                 16    15    .01  .003  .001  3    .003 .01  .005 >.05 >.05                    17    30    .03  .008  .003  3    .005 .008 .005 .008 >.05                                                                              >10                 18    50    .05  .03   .001  >10  .05  .03  .03  .03  >.05                                                                              >10                 19    50    .1   .05   .008  >10  .1             .03  >.05                                                                              >10                 20    30    >.1  .05   .0008 8    .03  .05  .05  .03  >.05                                                                              >10                 21    15    .03  .003  .003  5    .03  .003 .03  .01  >.05                                                                              .8                  22    5     .005 .001  .0003 3    .03  .001 .003 .01  >.05                    23    50    >.1  >.05  >.05       >.1            >.05 >.05                    24    30    .03  .01   .008  >10  .05  .03  .03  .03  >.05                                                                              >10                 25    40    >.1        .03   >10  >.1  >.1  .1   .03  >.05                                                                              >10                 26    20    .03  .005  .003  >10  .03  .03  .03  .05  >.05                                                                              >10                 27    15    .1   .05   .008  8    .1   .1   .05  .03  >.05                                                                              10                  28    30    .03  .005  .003  8    >.1  .08  .01  .008 .05 3                   29    50    .08  .01   .0008 8    .03  .03  .03  .01  >.05                                                                              >10                 30    30    >.1  >.05  >.05       >.1  >.1  >.1  >.05 >.05                    31    30    .1   >.05  .03   >10  .08  .05  .05  .03  >.05                                                                              >10                 32    8     .008 .0005 .0005 3    .01  .003 .05  .003 >.05                                                                              >10                 33    8     .03  .003  .001  3    .03  .003 .003 .005 >.05                                                                              >10                 34    30    .03  .003  .0008 3    .008 .01  .03  .005 >.05                                                                              3                   35    30    .01  .001  .001  3    .003 .001 .01  .005 >.05                                                                              >10                 36    8     .003 .003  .0003 3    .01  .03  .01  .008 >.05                                                                              >10                 37    9     .005 .008  .0003 3    .03  .003 .005 .005 .03 >10                 38    45    .03  .01   .001  8    .01  .01  .03  .01  >.05                                                                              >10                 39    25    .01  .03   .003  3    .03  .003 .008 .03  >.05                                                                              >10                 40    30    .03  .03   .003  >10  .03  .01  .03  .03  >.05                                                                              >10                 41    30    .08  .03   .008  8    .03  .03  .08  .01  >.05                                                                              >10                 42    25    .03  .003  .008  3    .008 .003 .03  .003 >.05                                                                              >10                 43    25    .03  .003  .008  3    .008 .03  .01  .008 >.05                                                                              >10                 44    30    .1   .05   .003  3    >.1  >.1  >.1  .03  >.05                                                                              1                   45    100   .1   >.05  .03   3    >.1            >.05 >.05                    46    90    .08  .03   .008  1    .1   >.1  .1   .05  >.05                                                                              3                   47    30    >.1        .008  3    >.1  >.1  .1   .05  >.05                                                                              8                   48    >100  >.1  >.05  .03   9    .1        >.1  .03  >.05                                                                              >10                 49    >100             >.05       >.1            >.05 >.05                    50    >100             >.05       >.1            >.05 >.05                    51    >100             > .05      >.1            >.05 >.05                    52    50    >.1  >.05  .03   8    >.1  >.1  >.1  >.05 >.05                    53    20    .05  .001  .0003 3    .03  .05  .01           >10                 54    5     .008 .003  .001  3    .03  .003 .01                               55    30    >.1  .05   .003  10   >.1                     >10                 56    5     .005 .003  .0008 3    .03  .08  .008          >10                 57    90    >.1  >.05  .003  5    >.1  >.1  >.1           >10                 58    15    >.1  >.05  .003  3    .08  .05  .03           >10                 59    40    >.1  .03   .001  3    .08  .08  .03  >.05 >.05                    __________________________________________________________________________

What is claimed is:
 1. Compounds corresponding to the formula ##EQU3##wherein R is selected from the group consisting of hydrogen, alkyl andaryl; R₁ is alkyl; R₂ is trifluoromethyl-substituted aryl; X is oxygen,sulfur or amino.
 2. A compound as set forth in claim 1 wherein X is O, Ris CH₃, R₁ is C₂ H₅ and R₂ is ##SPC1##
 3. A compound as set forth inclaim 1 wherein X is O, R is H, R₁ is C₂ H₅ and R₂ is ##SPC2##
 4. Acompound as set forth in claim 1 wherein X is O, R is H, R₁ is CH₃ andR₂ is ##SPC3##
 5. A compound as set forth in claim 1 wherein X is O, Ris CH₃, R₁ is CH₃ and R₂ is ##SPC4##